Evolution of size distribution, optical properties, and structure of Si nanoparticles obtained by laser-assisted fragmentation

We investigate the physical properties of Si-based nanoparticles produced by an environment-friendly three-step method relying on: (1) laser ablation of a solid target immersed in water, (2) centrifugation and separation, and (3) laser-assisted fragmentation. The evolution of size distribution is followed after each step by means of dynamic light scattering (DLS) measurements and crosschecked by transmission electron microscopy (TEM). The as-ablated colloidal suspension of Si nanoparticles presents a large size distribution, ranging from a few to hundreds of nanometers. Centrifugation drives the very large particles to the bottom eliminating them from the remaining suspension. Subsequent irradiation of height-separated suspensions with a second high-fluence (40 mJ/pulse) Nd:YAG laser operating at the fourth harmonic ( λ = 266 nm) leads to size reduction and ultra-small nanoparticles are obtainable depending on the starting size. Si nanoparticles as small as 1.5 nm with low dispersion ( ± 0.7 nm) are observed for the uppermost part after irradiation. These nanoparticles present a strong blue photoluminescence that remains stable for at least 8 weeks. Optical absorption (UV–Vis) measurements demonstrate an optical gap widening as a consequence of size decrease. Raman spectra present features related to pure silicon and silicon oxides for the irradiated sample. Interestingly, a defect band associated with silicon oxide is also identified, indicating the possible formation of defect states, which, in turn, supports the idea that the blue photoluminescence has its origin in defects.